CN117638120A - Supported catalyst and preparation method and application thereof - Google Patents
Supported catalyst and preparation method and application thereof Download PDFInfo
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- CN117638120A CN117638120A CN202410088811.5A CN202410088811A CN117638120A CN 117638120 A CN117638120 A CN 117638120A CN 202410088811 A CN202410088811 A CN 202410088811A CN 117638120 A CN117638120 A CN 117638120A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 120
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 81
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 64
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 51
- 239000011572 manganese Substances 0.000 claims abstract description 51
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 49
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 46
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 43
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 38
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000002156 mixing Methods 0.000 claims abstract description 35
- 238000000137 annealing Methods 0.000 claims abstract description 25
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 23
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 23
- 239000002131 composite material Substances 0.000 claims abstract description 22
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 22
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 18
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 229910000531 Co alloy Inorganic materials 0.000 claims abstract description 13
- 238000007598 dipping method Methods 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 53
- 238000010438 heat treatment Methods 0.000 claims description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 239000012298 atmosphere Substances 0.000 claims description 33
- 150000001875 compounds Chemical class 0.000 claims description 33
- 239000000460 chlorine Substances 0.000 claims description 31
- 229910052739 hydrogen Inorganic materials 0.000 claims description 28
- 239000002253 acid Substances 0.000 claims description 24
- 238000005245 sintering Methods 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 23
- 238000009766 low-temperature sintering Methods 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- 239000012018 catalyst precursor Substances 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 14
- 238000005580 one pot reaction Methods 0.000 claims description 14
- 230000009467 reduction Effects 0.000 claims description 14
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 13
- 239000004094 surface-active agent Substances 0.000 claims description 13
- 238000004321 preservation Methods 0.000 claims description 12
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 8
- 229920000877 Melamine resin Polymers 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 239000001569 carbon dioxide Substances 0.000 claims description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 7
- 239000000446 fuel Substances 0.000 claims description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
- 239000012528 membrane Substances 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 238000001179 sorption measurement Methods 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 6
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 229940099607 manganese chloride Drugs 0.000 claims description 6
- 235000002867 manganese chloride Nutrition 0.000 claims description 6
- 239000011565 manganese chloride Substances 0.000 claims description 6
- 238000005554 pickling Methods 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- -1 hydrogen ions Chemical class 0.000 claims description 5
- 238000001953 recrystallisation Methods 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 11
- 239000002243 precursor Substances 0.000 abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- 239000000377 silicon dioxide Substances 0.000 abstract description 5
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 5
- 230000010757 Reduction Activity Effects 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 abstract description 4
- 229910021581 Cobalt(III) chloride Inorganic materials 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- IEKWPPTXWFKANS-UHFFFAOYSA-K trichlorocobalt Chemical compound Cl[Co](Cl)Cl IEKWPPTXWFKANS-UHFFFAOYSA-K 0.000 abstract description 3
- 235000011167 hydrochloric acid Nutrition 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- RBVYPNHAAJQXIW-UHFFFAOYSA-N azanylidynemanganese Chemical compound [N].[Mn] RBVYPNHAAJQXIW-UHFFFAOYSA-N 0.000 abstract 1
- 238000005530 etching Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 description 19
- 238000003756 stirring Methods 0.000 description 19
- 239000000243 solution Substances 0.000 description 18
- 239000000047 product Substances 0.000 description 17
- 239000011259 mixed solution Substances 0.000 description 14
- 238000006722 reduction reaction Methods 0.000 description 13
- 229910002837 PtCo Inorganic materials 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 238000004502 linear sweep voltammetry Methods 0.000 description 10
- 238000001914 filtration Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 235000008373 pickled product Nutrition 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 229910000765 intermetallic Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910001339 C alloy Inorganic materials 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- PSHBJFRVFBSNAL-UHFFFAOYSA-N [Mn].[N].[C] Chemical compound [Mn].[N].[C] PSHBJFRVFBSNAL-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention belongs to the technical field of electrode catalysts, and particularly relates to a supported catalyst, and a preparation method and application thereof. The supported catalyst provided by the invention comprises a carrier and a platinum-cobalt alloy supported on the surface of the carrier; the carrier is mesoporous carbon doped with manganese and nitrogen; the molar ratio of the manganese to the mesoporous carbon is 1-50:1000. The invention firstly prepares Mn and N doped carbon powder coated by silicon dioxide, and then CO at high temperature 2 Etching to obtain manganese-nitrogen doped mesoporous carbon; then synthesizing Co/C through a continuous flow pipeline reactor, mixing Co/C, hydrochloric acid, ammonium chloride, ammonia water and hydrogen peroxide for reaction, then recrystallizing, forming hexaammine cobalt trichloride on the surface of Co/C, then dipping in a platinum source aqueous solution to obtain a Pt-Co composite precursor, and carrying out high-temperature treatment to order Pt-Co; and finally, annealing treatment is carried out. The platinum cobalt catalyst synthesized by the method has excellent stability and oxygen reduction activity.
Description
Technical Field
The invention belongs to the technical field of electrode catalysts, and particularly relates to a supported catalyst, and a preparation method and application thereof.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) can efficiently convert chemical energy in chemicals into electrical energy by means of an Oxygen Reduction Reaction (ORR), and no pollutant emissions are produced during the conversion process. However, the slow kinetics of the oxygen reduction reaction limit the use of PEMFCs to commercialize them. The oxygen reduction reaction efficiency is generally improved by adding a catalyst, and the existing catalyst mainly comprises Pt-based nano particles and high-surface-area carbon. However, pt-based catalysts undergo Pt dissolution, pt migration, and Pt agglomeration under acidic and high potential conditions, thereby affecting the electrochemical performance of proton exchange membrane fuel cells.
To solve the above problems, researchers have reduced the amount of platinum used by alloying platinum with transition metals such as Fe, co, ni, cu and Mn. These Pt-M alloy catalysts can increase the Mass Activity (MA) to a considerable level compared to pure Pt catalysts, but their rapid leaching of transition metal atoms in Pt-M alloy catalysts under acidic PEMFC corrosion leads to collapse of the catalyst framework, instability, especially for catalysts with heterogeneous particle size, which severely compromises their MA and ultimately the proton exchange membrane fuel cell life. How to improve the durability (stability) of the catalyst is a technical problem to be solved at present.
Disclosure of Invention
In view of the above, the invention provides a supported catalyst, a preparation method and application thereof, and the catalyst provided by the invention has excellent stability and oxygen reduction activity, and can be used as a proton exchange membrane fuel cell electrode catalyst to obviously improve electrochemical performance of a cell.
In order to solve the technical problems, the invention provides a supported catalyst, which comprises a carrier and a platinum-cobalt alloy supported on the surface of the carrier;
the carrier is mesoporous carbon doped with manganese and nitrogen; the molar ratio of the manganese to the mesoporous carbon is 1-50:1000.
Preferably, the molar ratio of the nitrogen to the mesoporous carbon is 1-50:1000.
Preferably, the platinum in the platinum-cobalt alloy accounts for 10-70% of the weight of the supported catalyst, and the molar ratio of the platinum to the cobalt in the platinum-cobalt alloy is 1-10:1.
The invention also provides a preparation method of the supported catalyst, which comprises the following steps:
mixing a carbon carrier, a manganese source, a nitrogen source, a surfactant, ethyl orthosilicate and water for adsorption to obtain a carbon-based compound;
sequentially performing low-temperature sintering and high-temperature sintering on the carbon-based composite to obtain manganese and nitrogen doped mesoporous carbon; the temperature of the low-temperature sintering is 750-850 ℃, and the low-temperature sintering is performed in a protective atmosphere; the high-temperature sintering temperature is 900-950 ℃, and the high-temperature sintering is performed in a carbon dioxide atmosphere;
mixing mesoporous carbon doped with manganese and nitrogen, cobalt chloride and ethylene glycol for reduction to obtain a Co/C compound;
mixing the Co/C compound, hydrochloric acid, ammonium chloride, activated carbon, ammonia water and hydrogen peroxide to perform one-pot reaction, and then mixing with concentrated hydrochloric acid to perform recrystallization to obtain [ Co (NH) 3 ) 6 ]Cl 3 @Co/C; the molar ratio of the hydrogen ions to the Co/C compound in the system after the Co/C compound, hydrochloric acid, ammonium chloride, activated carbon, ammonia water and hydrogen peroxide are mixed is 0.1-1:1; the mole ratio of chloride ions to Co/C complex in the system after the one-pot reaction and the concentrated hydrochloric acid are mixed is 0.2-2:1;
the [ Co (NH) 3 ) 6 ]Cl 3 Mixing @ Co/C, a chlorine-containing platinum source and water, and then dipping and evaporating to dryness to obtain a catalyst precursor;
and (3) annealing the catalyst precursor to obtain the supported catalyst.
Preferably, the manganese source comprises manganese chloride, the nitrogen source comprises melamine, the water is deionized water, and the surfactant comprises trimethyl 1-hexadecyl ammonium bromide or polyoxyethylene polyoxypropylene ether;
the molar ratio of the carbon carrier to the manganese source to the nitrogen source to the water is 1:0.001-0.05:0.001-0.05:1-40;
the molar ratio of the surfactant to the carbon carrier is 0.001-0.05:1;
the molar ratio of the ethyl orthosilicate to the carbon carrier is 0.1-5:1.
Preferably, the heating rate of the low-temperature sintering is 4-6 ℃/min, and the heat preservation time of the low-temperature sintering is 2-3 h;
the temperature rising rate of rising to the temperature required by high-temperature sintering is 4-6 ℃/min, and the heat preservation time of the high-temperature sintering is 2-3 h;
the molar ratio of the manganese and nitrogen doped mesoporous carbon to the cobalt chloride is 100-5:1;
the reduction is continuous flow microwave reduction, and the flow speed of the continuous flow microwave reduction is 50-500 mL/min.
Preferably, the mass ratio of the ammonium chloride to the Co/C composite is 1:1-10;
the mass ratio of the active carbon to the Co/C composite is 1:1-5;
the mass ratio of the ammonia water to the hydrogen peroxide to the Co/C composite is 1-5:1.
Preferably, the chloroplatinic acid source comprises chloroplatinic acid, potassium chloroplatinate, ammonium hexachloroplatinate, potassium chloroplatinic acid, ammonium chloroplatinic acid, or sodium chloroplatinic acid;
the chlorine-containing platinum source and [ Co (NH) 3 ) 6 ]Cl 3 The mass ratio of @ Co/C is 10-1:1.
Preferably, the temperature of the annealing treatment is 700-800 ℃, the heating rate from the temperature rise to the temperature required by the annealing treatment is 3-6 ℃/min, and the heat preservation time of the annealing treatment is 3-4 h; the annealing treatment is carried out in a mixed atmosphere of hydrogen and nitrogen, wherein the volume content of the hydrogen in the mixed atmosphere of the hydrogen and the nitrogen is 10-20%;
the annealing treatment further comprises the following steps:
sequentially carrying out acid washing and heat treatment on the annealed product to obtain the supported catalyst;
the pickling is to soak the annealed product in a nitric acid solution for 1-3 hours;
the temperature of the heat treatment is 380-420 ℃, the heating rate from the temperature required by the heat treatment to the temperature required by the heat treatment is 5-10 ℃/min, and the heat preservation time of the heat treatment is 2-3 h; the heat treatment is performed in a mixed atmosphere of hydrogen and nitrogen, and the volume content of the hydrogen in the mixed atmosphere of the hydrogen and the nitrogen is 10-20%.
The invention also provides application of the supported catalyst in proton exchange membrane fuel cells or the supported catalyst prepared by the preparation method in the technical scheme.
The invention provides a supported catalyst, which comprises a carrier and a platinum-cobalt alloy supported on the surface of the carrier; the carrier is mesoporous carbon doped with manganese and nitrogen; the molar ratio of the manganese to the mesoporous carbon is 1-50:1000. The catalyst provided by the invention has excellent stability.
The invention firstly prepares Mn and N doped carbon powder coated by silicon dioxide, and then passes CO at high temperature 2 The Mn and N doped mesoporous carbon which are mutually communicated is obtained; then synthesizing Co/C through a continuous flow pipeline reactor, mixing Co/C, hydrochloric acid, ammonium chloride, ammonia water and hydrogen peroxide for reaction, and then recrystallizing to form hexaammine cobalt trichloride on the surface of Co/C so as to uniformly impregnate a chlorine-containing platinum source subsequently; will [ Co (NH) 3 ) 6 ]Cl 3 Impregnating the @ Co/C in a chlorine-containing platinum source aqueous solution to obtain a Pt-Co composite precursor, and then carrying out high-temperature treatment to order the Pt-Co; then acid washing is carried out to remove redundant Co and increase hydroxyl on the surface of the carbon carrier so as to improve the hydrophilicity of the carbon carrier; finally, the thermodynamic instability is eliminated by annealing, and Pt-skin is induced. The platinum-cobalt catalyst synthesized by the method has excellent stability and oxygen reduction activity, adjustable atomic ratio of Pt and Co and potential for large-scale production.
Drawings
FIG. 1 is an SEM image of a manganese and nitrogen doped mesoporous carbon prepared in example 1;
FIG. 2 is a BET plot of manganese and nitrogen doped mesoporous carbon prepared in example 1;
FIG. 3 is an XRD spectrum of the supported catalyst prepared in example 1;
FIG. 4 is a TEM image of the supported catalyst prepared in example 1;
FIG. 5 is a graph showing LSV curves of the supported catalyst prepared in example 1, the supported catalyst prepared in comparative example 1, and the commercially available TKK-Pt/C catalyst;
FIG. 6 is a graph showing LSV comparison after 30000 cycles of initial run and recycle of the supported catalyst prepared in example 1 of the present invention.
Detailed Description
The invention provides a supported catalyst, which comprises a carrier and a platinum-cobalt alloy supported on the surface of the carrier;
the carrier is mesoporous carbon doped with manganese and nitrogen.
In the invention, the molar ratio of the manganese to the mesoporous carbon is 1-50:1000, preferably 4-10:1000; the molar ratio of nitrogen to mesoporous carbon is preferably 1-50:1000, more preferably 5-20:1000.
In the invention, the platinum accounts for 10-70% of the weight of the supported catalyst in the platinum-cobalt alloy, and more preferably 20-60%; the molar ratio of platinum to cobalt in the platinum-cobalt alloy is preferably 1-10:1, more preferably 2-9:1.
The invention also provides a preparation method of the supported catalyst, which comprises the following steps:
mixing a carbon carrier, a manganese source, a nitrogen source, a surfactant, ethyl orthosilicate and water for adsorption to obtain a carbon-based compound;
sequentially performing low-temperature sintering and high-temperature sintering on the carbon-based composite to obtain manganese and nitrogen doped mesoporous carbon; the temperature of the low-temperature sintering is 750-850 ℃, and the low-temperature sintering is performed in a protective atmosphere; the high-temperature sintering temperature is 900-950 ℃, and the high-temperature sintering is performed in a carbon dioxide atmosphere;
mixing mesoporous carbon doped with manganese and nitrogen, cobalt chloride and ethylene glycol for reduction to obtain a Co/C compound;
mixing the Co/C compound, hydrochloric acid, ammonium chloride, activated carbon, ammonia water and hydrogen peroxide to perform one-pot reaction, and then mixing with concentrated hydrochloric acid to perform recrystallization to obtain [ Co (NH) 3 ) 6 ]Cl 3 @Co/C; the molar ratio of the hydrogen ions to the Co/C compound in the system after the Co/C compound, hydrochloric acid, ammonium chloride, activated carbon, ammonia water and hydrogen peroxide are mixed is 0.1-1:1; the mole ratio of chloride ions to Co/C complex in the system after one-pot reaction and concentrated hydrochloric acid mixing is as follows0.2~2:1；
The [ Co (NH) 3 ) 6 ]Cl 3 Mixing @ Co/C, a chlorine-containing platinum source and water, and then dipping and evaporating to dryness to obtain a catalyst precursor;
and (3) annealing the catalyst precursor to obtain the supported catalyst.
The invention mixes and adsorbs a carbon carrier, a manganese source, a nitrogen source, a surfactant, tetraethoxysilane and water to obtain a carbon-based compound. In the present invention, the mixing preferably includes the steps of:
firstly mixing a carbon carrier, a manganese source, a nitrogen source and water to obtain a first mixed solution;
dispersing a surfactant in the first mixed solution to obtain a second mixed solution;
and carrying out second mixing on the tetraethoxysilane and the second mixed solution.
The method comprises the step of first mixing a carbon carrier, a manganese source, a nitrogen source and water to obtain a first mixed solution. In the present invention, the carbon support preferably comprises a VXC-72 carbon support or an EC-300 carbon support, more preferably a VXC-72 carbon support. In the present invention, the manganese source preferably includes manganese chloride; the nitrogen source preferably comprises melamine; the water is preferably deionized water. In the invention, the molar ratio of the carbon carrier, the manganese source, the nitrogen source and the water is preferably 1:0.001-0.05:1:0.001-0.05:1-40, more preferably 1:0.01-0.03:1:0.01-0.03:1-15. The invention has no special requirement on the first mixing, so long as the first mixing can be uniformly mixed.
After the first mixed solution is obtained, the surfactant is dispersed in the first mixed solution to obtain a second mixed solution. In the present invention, the surfactant preferably includes trimethyl 1-hexadecyl ammonium bromide (CTAB) or polyoxyethylene polyoxypropylene ether, more preferably trimethyl 1-hexadecyl ammonium bromide. In the present invention, the molar ratio of the surfactant to the carbon carrier is preferably 0.001 to 0.05:1, more preferably 0.005 to 0.02:1.
In the invention, the dispersion is preferably performed under ultrasonic conditions, and the ultrasonic time is preferably 20-40 min, more preferably 25-35 min. The invention has no special requirement on the ultrasonic power, and the ultrasonic power can be uniformly dispersed.
After the second mixed solution is obtained, the invention carries out second mixing on Tetraethoxysilane (TEOS) and the second mixed solution. The pH value of the second mixed solution is preferably adjusted to 10-11 before the second mixing; the pH adjustor for adjusting the pH is preferably aqueous ammonia. The invention adjusts the pH value of the second mixed solution in the above range, which is beneficial to the hydrolysis of tetraethoxysilane to form silicon dioxide. In the invention, the molar ratio of the tetraethoxysilane to the carbon carrier is preferably 0.1-5:1, more preferably 0.2-2:1. The invention has no special requirement on the second mixing, so long as the second mixing can be uniformly mixed.
In the present invention, the adsorption is preferably performed under stirring, and the stirring time is preferably 8 to 12 hours, more preferably 9 to 11 hours.
In the present invention, the adsorption step preferably further comprises: and (3) carrying out solid-liquid separation on the system after adsorption, and drying the solid obtained by the solid-liquid separation to obtain the carbon-based compound. In the present invention, the solid-liquid separation is preferably centrifugation. The present invention is not particularly limited to the centrifugation. The present invention has no special requirement for the drying, as long as the solvent can be removed. In the present invention, the carbon-based composite includes a carbon support and manganese chloride, melamine, trimethyl 1-hexadecyl ammonium bromide and silica adsorbed to the surface of the carbon support.
After obtaining the carbon-based composite, the invention sequentially carries out low-temperature sintering and high-temperature sintering on the carbon-based composite to obtain the manganese and nitrogen doped mesoporous carbon. In the invention, the low-temperature sintering temperature is 750-850 ℃, preferably 780-800 ℃; the heating rate for heating to the temperature required by low-temperature sintering is preferably 4-6 ℃/min, more preferably 5 ℃/min; the heat preservation time of the low-temperature sintering is preferably 2-3 hours. In the invention, the low-temperature sintering is performed under a protective atmosphere; the protective atmosphere is preferably nitrogen or argon, more preferably nitrogen. The invention uses low-temperature sintering to make melamine become nitrogen, and removes the surface active agent absorbed on the surface of the carbon-based compound; and simultaneously, combining manganese ions and carbon to form manganese nitrogen carbon.
In the invention, the high-temperature sintering temperature is 900-950 ℃, preferably 920-940 ℃; the heating rate for heating to the temperature required by high-temperature sintering is preferably 4-6 ℃/min, more preferably 5 ℃/min; the heat preservation time of the high-temperature sintering is preferably 2-3 hours. The invention preferably continues to raise the temperature to the temperature required by high-temperature sintering on the basis of low-temperature sintering temperature. In the present invention, the high-temperature sintering is performed under a carbon dioxide atmosphere. The invention preferably increases the temperature from the low-temperature sintering temperature to the temperature required by high-temperature sintering under the protective atmosphere. The invention can utilize carbon dioxide atmosphere to etch and expand pores (carbon dioxide reacts with carbon) to form mesopores by high-temperature sintering under the carbon dioxide atmosphere.
In the present invention, the high-temperature sintering preferably further comprises: cooling the product after high-temperature sintering to room temperature and then carrying out acid washing; and drying the acid-washed product to obtain the manganese and nitrogen doped mesoporous carbon. In the present invention, the temperature of the room temperature is preferably 20 to 35 ℃, more preferably 25 to 30 ℃. The invention has no special requirements on the cooling mode. In the invention, the acid washing is preferably to soak the product after high-temperature sintering in an acid solution; the acid solution is preferably hydrofluoric acid solution; the molar concentration of the acid solution is preferably 1mol/L. In the invention, the soaking temperature is preferably 75-85 ℃, more preferably 80 ℃; the soaking time is preferably 3-12 hours, more preferably 5-10 hours. The invention can remove silicon dioxide by acid washing to realize reaming, and can improve the inherent activity and stability of mesoporous carbon doped with manganese and nitrogen.
After the mesoporous carbon doped with manganese and nitrogen is obtained, the mesoporous carbon doped with manganese and nitrogen, cobalt chloride and ethylene glycol are mixed for reduction to obtain the Co/C compound. In the invention, the molar ratio of the mesoporous carbon doped with manganese and nitrogen to the cobalt chloride is preferably 100-5:1, more preferably 90-10:1. In the present invention, the mixing is preferably performed under ultrasonic conditions; the time of the ultrasonic treatment is preferably 20-30 min, more preferably 22-28 min. The invention has no special requirement on the ultrasonic power, and can be uniformly mixed. In the invention, the glycol is both a solvent and a reducing agent, and can be used as the reducing agent to reduce cobalt chloride into cobalt; and cobalt chloride is uniformly dispersed on the surface of the mesoporous carbon in the mixing process.
In the invention, the reduction is preferably continuous flow microwave reduction, and the flow rate of the continuous flow microwave reduction is preferably 50-500 mL/min, more preferably 100-400 mL/min. In the present invention, the continuous flow microwave reduction is preferably performed in a microwave pipeline reactor.
In the present invention, the reduced material preferably further comprises: and (3) carrying out solid-liquid separation on the reduced system, washing the solid obtained by the solid-liquid separation with water, and drying to obtain the Co/C compound. In the present invention, the solid-liquid separation is preferably filtration. The invention has no special requirement on the filtration, and can be realized by adopting a conventional mode in the field. In the present invention, the water for washing is preferably deionized water. The invention has no special requirement on the drying, and can be realized by adopting a conventional mode in the field.
After the Co/C compound is obtained, the invention mixes the Co/C compound, hydrochloric acid, ammonium chloride, activated carbon, ammonia water and hydrogen peroxide to carry out one-pot reaction, and then mixes the mixture with concentrated hydrochloric acid to carry out recrystallization to obtain [ Co (NH) 3 ) 6 ]Cl 3 @ Co/C. In the invention, the mixing of the Co/C compound, hydrochloric acid, ammonium chloride, activated carbon, ammonia water and hydrogen peroxide preferably comprises the following steps:
thirdly mixing the Co/C compound, hydrochloric acid and ammonium chloride to obtain a third mixture;
adding activated carbon into the third mixture, and then adding ammonia water and hydrogen peroxide.
The Co/C compound, hydrochloric acid and ammonium chloride are mixed for the third time to obtain a third mixture. In the invention, the mass ratio of the ammonium chloride to the Co/C composite is preferably 1:1-10, more preferably 1:1-5. In the present invention, the third mixing is preferably performed under stirring; the temperature of stirring is preferably 40-60 ℃, more preferably 45-55 ℃; the stirring time is preferably 10 to 30min, more preferably 15 to 25min. In the third mixing process, the hydrochloric acid and part of cobalt in the Co/C compound are subjected to oxidation-reduction reaction to generate cobalt ions.
After a third mixture is obtained, the invention adds the activated carbon into the third mixture and then adds ammonia water and hydrogen peroxide. In the invention, the mass ratio of the active carbon to the Co/C composite is preferably 1:1-5, and more preferably 1:1-3. In the invention, the temperature for adding the activated carbon is preferably 5-15 ℃, more preferably 8-12 ℃. In the present invention, the activated carbon mainly functions as a catalyst.
In the invention, the mass ratio of the ammonia water, the hydrogen peroxide and the Co/C composite is preferably 1-5:1, more preferably 2-5:2-5:1. The invention has no special requirement on the mode of adding ammonia water and hydrogen peroxide, and can be uniformly mixed.
In the invention, the molar ratio of the hydrogen ions to the Co/C compound in the mixed system of the Co/C compound, hydrochloric acid, ammonium chloride, activated carbon, ammonia water and hydrogen peroxide is 0.1-1:1, preferably 0.3-0.6:1.
In the invention, the temperature of the one-pot reaction is preferably 50-70 ℃, more preferably 55-65 ℃; stirring is preferably carried out in the one-pot reaction process, and the stirring time is preferably 10-40 min, more preferably 20-30 min.
In the present invention, the one-pot reaction preferably further comprises: the catalyst in the system after one-pot reaction is removed. The method has no special requirement on the mode of removing the catalyst, and can be adopted by the conventional mode in the field.
In the invention, the mass fraction of the concentrated hydrochloric acid is 37%; the molar ratio of chloride ions to Co/C complex in the mixed system obtained by mixing the one-pot reaction system and the concentrated hydrochloric acid is 0.2-2:1, preferably 0.4-0.8:1.
In the present invention, the recrystallized product preferably further comprises: subjecting the recrystallized system to solid-liquid separation, washing and drying the solid obtained by the solid-liquid separation to obtain [ Co (NH) 3 ) 6 ]Cl 3 @ Co/C. In the present invention, the solid-liquid separation is preferably filtration. The present invention has no special requirement for the drying, as long as the solvent can be removed.
The invention is adsorbed on the surface of Co/C compound through one-pot reaction and recrystallization of hexaammine cobalt trichloride.
To obtain [ Co (NH) 3 ) 6 ]Cl 3 After @ Co/C, the invention combines the [ Co (NH) 3 ) 6 ]Cl 3 And (3) mixing the @ Co/C, the chlorine-containing platinum source and water, and then dipping and evaporating to dryness to obtain a catalyst precursor. In the present invention, the chloroplatinic acid-containing source preferably includes chloroplatinic acid, potassium chloroplatinate, ammonium hexachloroplatinate, potassium chloroplatinate, ammonium chloroplatinate or sodium chloroplatinate, more preferably chloroplatinic acid or sodium chloroplatinate. In the present invention, the chlorine-containing platinum source and [ Co (NH) 3 ) 6 ]Cl 3 The mass ratio of @ Co/C is preferably 10-1:1, more preferably 8-2:1. In the invention, the mixing is preferably performed under ultrasonic conditions, and the ultrasonic time is preferably 30-40 min, more preferably 33-38 min. In the present invention, the impregnation and evaporation to dryness is preferably accompanied by stirring; the temperature of stirring is preferably 40-80 ℃, more preferably 50-70 ℃; the stirring time is not particularly required, and the stirring is carried out until the system is in a viscous state. The catalyst precursor is preferably obtained by drying the system after stirring to be viscous for 10-12 hours. The invention preferably regulates and controls the platinum loading by regulating the times of soaking and evaporating.
In the present invention, [ Co (NH) 3 ) 6 ]Cl 3 Co (NH) 3 ) 6 ] 3+ Can combine Co orientation [ PtCl ] 4 ] 2- Or [ PtCl ] 6 ] 2- Thereby forming a PtCo alloy. The invention can regulate and control the atomic ratio of Pt and Co in the catalyst by regulating and controlling the addition of the chlorine-containing platinum source.
After the catalyst precursor is obtained, the invention carries out annealing treatment on the catalyst precursor to obtain the supported catalyst. In the invention, the temperature of the annealing treatment is preferably 700-800 ℃, more preferably 750-780 ℃; the heating rate for heating to the temperature required by the annealing treatment is preferably 3-6 ℃/min, more preferably 4-5 ℃; the heat preservation time of the annealing treatment is preferably 3-4 hours; the annealing treatment is preferably performed under a mixed atmosphere of hydrogen and nitrogen, and the volume content of hydrogen in the mixed atmosphere of hydrogen and nitrogen is preferably 10-20%, more preferably 13-15%.
The invention forms platinum-cobalt alloy in the catalyst precursor through annealing treatment.
In the present invention, the annealing treatment preferably further comprises:
and (3) sequentially carrying out acid washing and heat treatment on the annealed product to obtain the supported catalyst.
In the present invention, the acid washing is preferably performed by immersing the annealed product in a nitric acid solution. In the invention, the molar concentration of the nitric acid solution is preferably 0.1-5 mol/L, more preferably 0.5-4 mol/L; the soaking temperature is preferably 80-90 ℃, more preferably 85-88 ℃; the soaking time is preferably 1-3 hours, more preferably 2 hours. The invention can remove residual cobalt on the surface of the platinum-cobalt alloy and the surface of the mesoporous carbon through acid washing.
In the present invention, the acid-washed steel sheet preferably further comprises: washing the pickled product with water and drying. In the present invention, the water for washing is preferably deionized water. The drying is not particularly limited as long as the solvent can be removed.
In the invention, the temperature of the heat treatment is preferably 380-420 ℃, more preferably 400 ℃; the heating rate for heating to the temperature required by the heat treatment is preferably 5-10 ℃/min, more preferably 6-8 ℃/min, and the heat preservation time of the heat treatment is preferably 2-3 h, more preferably 2.3-2.5 h; the heat treatment is preferably performed under a mixed atmosphere of hydrogen and nitrogen, and the volume content of hydrogen in the mixed atmosphere of hydrogen and nitrogen is preferably 10-20%, more preferably 12-15%. In the present invention, the heat treatment is preferably performed in a tube furnace. The invention eliminates defects formed in the pickling process by heat treatment and improves the thermodynamic stability of the catalyst.
In the present invention, the heat-treated material preferably further comprises: and (3) placing the heat-treated product in a pulverizer for pulverizing to obtain the supported catalyst. In the present invention, the pulverizing time is preferably 5 to 30 seconds, more preferably 10 to 20 seconds.
The invention firstly prepares Mn and N doped carbon-silicon compound, and introduces N at high temperature 2 And CO 2 Preparing mesoporous on the surface of the carbon carrier in a directional way to obtain interpenetrating mesoporous carbon; co/C is prepared on the surface of a carbon carrier by adopting a continuous pipeline method, and Co particles are caused by high-temperature treatmentDensification; adding HCl and ammonia water solution to form [ Co (NH) 3 ) 6 ]Cl 3 @Co/C; the above [ Co (NH) 3 ) 6 ]Cl 3 Preparing a composite precursor by adopting a multi-impregnation method by taking Co/C, chloroplatinic acid and the like as raw materials; and carrying out heat treatment and acid washing on the composite precursor to obtain the mesoporous carbon supported PtCo intermetallic compound catalyst. The platinum-cobalt catalyst synthesized by the method has excellent stability and oxygen reduction activity and has the potential of large-scale production.
The invention also provides application of the supported catalyst in proton exchange membrane fuel cells or the supported catalyst prepared by the preparation method in the technical scheme.
The technical solutions provided by the present invention are described in detail below in conjunction with examples for further illustrating the present invention, but they should not be construed as limiting the scope of the present invention.
Example 1
S1: weighing 10g (0.84 mol) of VXC-72 carbon carrier, 0.5 g (0.004 mol) of manganese chloride, 2.5 g (0.02 mol) of melamine and 200 mL of deionized water to prepare an aqueous solution; then add CTAB of 2g (0.0055 mol) to the inside and ultrasonic for 40min; then, after the pH value is adjusted to 10 by ammonia water, 100 mL (0.45 mol) TEOS is added into the mixture; finally, stirring 12h, centrifugally washing and drying to obtain a carbon-based compound;
s2: 10g of the carbon-based composite prepared in S1 was placed in a tube furnace under N 2 Heating to 800 ℃ at a speed of 5 ℃/min under the atmosphere, and preserving heat for 2 hours; then heating to 900 ℃ at a rate of 4 ℃/min; subsequently, switch to CO 2 Atmosphere, keep warm 2h; finally, cooling to normal temperature, pickling 8 h under the conditions of 80 ℃ and 1mol/L hydrofluoric acid, filtering and drying to obtain manganese and nitrogen doped mesoporous carbon;
s3: weighing 10g of mesoporous carbon doped with manganese and nitrogen of S2 and 4.2g of cobalt chloride, dissolving in ethylene glycol, performing ultrasonic dispersion for 20min, then passing through a continuous flow microwave pipeline reactor at a flow rate of 100 mL/min, washing with deionized water, filtering, and drying to obtain a Co/C compound;
s4: 5 g of the Co/C complex obtained in S3 is weighed and dispersed into deionized water, 20mL hydrochloric acid and 1 g ammonium chloride are added into the solution, the solution is stirred for 10 minutes at 60 ℃ (the molar ratio of hydrogen ions to Co/C complex in the mixed system is 0.5:1), meanwhile, 2g of active carbon is added, and then the solution is cooled to 5 ℃; secondly, adding 10 mL ammonia water with the concentration of 1mol/L and 15mL hydrogen peroxide, and stirring for 30min at 50 ℃ to perform one-pot reaction; adding concentrated hydrochloric acid with the mass concentration of 10 mL of 37wt% after removing the active carbon, and generating precipitate immediately after adding the concentrated hydrochloric acid, wherein the mol ratio of chloride ions to Co/C complex in the mixed solution is 0.4:1; finally, the precipitate is filtered, washed and dried to obtain [ Co (NH) 3 ) 6 ]Cl 3 @Co/C；
S5: 5 g of S4 was weighed out to give [ Co (NH) 3 ) 6 ]Cl 3 Dispersing @ Co/C into 50 mL deionized water and adding 10g H 2 PtCl 6 ·6H 2 O, ultrasonic treatment is carried out for 30min, and stirring and evaporation are carried out at 50 ℃ until the mixture is in a viscous state; then placing the catalyst into a vacuum drying oven to be dried 12h, thus obtaining a catalyst precursor;
s6: the catalyst precursor of S5 is placed in a tube furnace for high-temperature annealing, and then H is the catalyst precursor 2 /N 2 (10%H 2 ) Heating to 700 ℃ at a speed of 5 ℃/min under the atmosphere, and preserving heat for 4h to obtain an annealed product;
s7: placing the annealed product in S6 into a nitric acid solution with the temperature of 80 ℃ and the mol/L of 1 to be pickled for 2h, washing and filtering with deionized water, and drying to obtain a pickled product;
s8: placing the pickled product described in S7 in a tube furnace, and heating in H 2 /N 2 (10%H 2 ) Heating to 400 ℃ at a speed of 5 ℃/min under the atmosphere, and preserving heat for 2h to obtain a heat treatment product;
s9: grinding and crushing, placing a fully-closed crusher in a low-temperature test box, putting the heat treatment product into the crusher to crush 30s, and then taking out to obtain the uniformly-ground supported catalyst which is named as Pt@PtCo/C alloy catalyst.
Example 2
S1: 10g (0.84 mol) of EC-300 carbon carrier, 0.5 g (0.004 mol) of manganese chloride, 2.5 g (0.02 mol) of melamine and 200 mL of deionized water are weighed to prepare an aqueous solution; then add CTAB of 2g (0.0055 mol) to the inside and ultrasonic for 40min; then, after the pH value is adjusted to 10 by ammonia water, 100 mL (0.45 mol) TEOS is added into the mixture; finally, stirring 12h, centrifugally washing and drying to obtain a carbon-based compound;
s2: 10g of the carbon-based composite prepared in S1 was placed in a tube furnace under N 2 Heating to 700 ℃ at a speed of 5 ℃/min under the atmosphere, and preserving heat for 2 hours; then heating to 900 ℃ at a rate of 5 ℃/min; subsequently, switch to CO 2 Atmosphere, keep warm 3h; finally, cooling to normal temperature, pickling 8 h under the conditions of 80 ℃ and 1mol/L hydrofluoric acid, filtering and drying to obtain manganese and nitrogen doped mesoporous carbon;
s3: weighing 10g of mesoporous carbon doped with manganese and nitrogen and 8.4 g of cobalt chloride, dissolving in ethylene glycol, performing ultrasonic dispersion for 20min, then passing through a continuous flow microwave pipeline reactor at a flow rate of 50 mL/min, washing with deionized water, filtering, and drying to obtain a Co/C composite;
s4: 6 g of the Co/C complex obtained in S3 is weighed and dispersed into deionized water, 20mL hydrochloric acid and 1 g ammonium chloride are added into the solution, the solution is stirred for 10 min at 60 ℃, 2g of active carbon is added, and then the solution is cooled to 5 ℃; secondly, adding 15mL mol/L ammonia water and 20mL hydrogen peroxide, and stirring for 40min at 70 ℃; adding concentrated hydrochloric acid with the mass concentration of 12 mL of 37wt% after removing the active carbon, and generating precipitate immediately after adding the concentrated hydrochloric acid, wherein the mol ratio of chloride ions to Co/C complex in the mixed solution is 0.5:1; finally, the precipitate is filtered, washed and dried to obtain [ Co (NH) 3 ) 6 ]Cl 3 @Co/C；
S5: 5 g of S4 was weighed out to give [ Co (NH) 3 ) 6 ]Cl 3 Dispersing @ Co/C into 50 mL deionized water and adding 15 g H 2 PtCl 6 ·6H 2 O, ultrasonic treatment is carried out for 30min, and stirring and evaporation are carried out at 60 ℃ until the mixture is in a viscous state; then placing the catalyst into a vacuum drying oven to be dried 12h, thus obtaining a catalyst precursor;
s6: the catalyst precursor of S5 is placed in a tube furnace for high-temperature annealing, and then H is the catalyst precursor 2 /N 2 (10%H 2 ) Heating to 800 ℃ at a speed of 3 ℃/min under the atmosphere, and preserving heat for 4h to obtain an annealed product;
s7: placing the annealed product in S6 into a nitric acid solution with the temperature of 80 ℃ and the mol/L of 1 to be pickled for 2h, washing and filtering with deionized water, and drying to obtain a pickled product;
s8: placing the pickled product described in S7 in a tube furnace, and heating in H 2 /N 2 (10%H 2 ) Heating to 400 ℃ at a speed of 5 ℃/min under the atmosphere, and preserving heat for 2h to obtain a heat treatment product;
s9: grinding and crushing, namely placing a fully-closed crusher in a low-temperature test box, and carrying out heat treatment on the blocky products; crushing 30 to s in a crusher, and taking out to obtain the Pt@PtCo/C alloy catalyst which is uniformly grinded.
Comparative example 1
S1: 10g of VXC-72, 26.5 g of H are reacted 2 PtCl 6 ·6H 2 O and 4.2g CoCl 2 ·6H 2 Mixing O with 150 mL absolute ethyl alcohol, dipping and stirring the mixture, and removing the solvent by a rotary evaporator to obtain uniformly mixed precursor powder;
s2: drying the precursor powder in a transfer oven, transferring to a quartz crucible, placing into a tube furnace, and adding H 2 /N 2 (10%H 2 ) Raising the temperature of the powder precursor to 700 ℃ at 5 ℃/min under the atmosphere, and keeping the temperature of the powder precursor at 2h; naturally cooling to room temperature to obtain a low-order pretreated PtCo/C catalyst;
s3: the PtCo/C catalyst is pretreated, is placed in a nitric acid solution with the temperature of 80 ℃ and the temperature of 1M for pickling for 2h, is washed and filtered by deionized water, and is dried to obtain the PtCo/C catalyst.
Scanning electron microscopy detection is carried out on the mesoporous carbon doped with manganese and nitrogen and prepared in the embodiment 1, so that an SEM image is obtained, and the SEM image is shown in figure 1. It can be seen from fig. 1 that the prepared mesoporous carbon doped with manganese and nitrogen has a plurality of pore structures on the surface.
The mesoporous carbon doped with manganese and nitrogen prepared in example 1 was subjected to nitrogen adsorption detection, and the BET graph is shown in FIG. 2. It can be seen from FIG. 2 that the average pore diameter of the prepared manganese and nitrogen doped mesoporous carbon was 5nm.
XRD detection was performed on the supported catalyst prepared in example 1, and an XRD spectrum was obtained as shown in FIG. 3. From fig. 3, superlattice peaks of PtCo ordered structure can be seen, indicating successful preparation of PtCo intermetallic compound.
Transmission electron microscopy was performed on the supported catalyst prepared in example 1 to obtain a TEM image, as shown in fig. 4. FIG. 4 shows that PtCo intermetallic compound is uniformly dispersed on commercial carbon black, and the average particle size is 3.6nm.
The supported catalyst (Pt@PtCo/C) prepared in example 1, the supported catalyst (PtCo/C) prepared in comparative example 1 and commercially available TKK-Pt/C commercial catalyst having a mass fraction of 50% were subjected to electrochemical testing according to a linear sweep voltammetry, respectively, to obtain LSV curves, as shown in FIG. 5. As can be seen from FIG. 5, the initial mass activity of the supported catalyst prepared in example 1 was as high as 668 mA/mg, which is far superior to that of the commercial catalyst (mass fraction: 50% TKK-Pt/C, mass activity: 135 mA/mg) and the catalyst of comparative example 1 (mass activity: 318.7 mA/mg). Electrochemical tests were carried out on the supported catalyst prepared in example 2 according to linear sweep voltammetry, and the initial mass activity of the supported catalyst was 597.6 mA/mg.
The supported catalyst prepared in example 1 was subjected to electrochemical stability test to obtain LSV curve as shown in fig. 6. The curves in fig. 6 are an LSV curve for initial operation and an LSV curve after 30000 cycles, respectively, and the LSV result shows that the half-wave potential on the LSV is reduced by 8mv and the Mass Activity (MA) retention rate at 0.9V is 90.1% before and after the stability test, indicating that the supported catalyst provided by the invention has excellent stability and excellent activity.
Although the foregoing embodiments have been described in some, but not all, embodiments of the invention, it should be understood that other embodiments may be devised in accordance with the present embodiments without departing from the spirit and scope of the invention.
Claims (10)
1. A supported catalyst characterized by comprising a carrier and a platinum-cobalt alloy supported on the surface of the carrier;
the carrier is mesoporous carbon doped with manganese and nitrogen; the molar ratio of the manganese to the mesoporous carbon is 1-50:1000.
2. The supported catalyst of claim 1, wherein the molar ratio of nitrogen to mesoporous carbon is 1-50:1000.
3. The supported catalyst according to claim 1, wherein the platinum-cobalt alloy comprises 10-70% by mass of platinum in the supported catalyst, and the molar ratio of platinum to cobalt in the platinum-cobalt alloy is 1-10:1.
4. A method for preparing the supported catalyst according to any one of claims 1 to 3, comprising the steps of:
mixing a carbon carrier, a manganese source, a nitrogen source, a surfactant, ethyl orthosilicate and water for adsorption to obtain a carbon-based compound;
sequentially performing low-temperature sintering and high-temperature sintering on the carbon-based composite to obtain manganese and nitrogen doped mesoporous carbon; the temperature of the low-temperature sintering is 750-850 ℃, and the low-temperature sintering is performed in a protective atmosphere; the high-temperature sintering temperature is 900-950 ℃, and the high-temperature sintering is performed in a carbon dioxide atmosphere;
mixing mesoporous carbon doped with manganese and nitrogen, cobalt chloride and ethylene glycol for reduction to obtain a Co/C compound;
mixing the Co/C compound, hydrochloric acid, ammonium chloride, activated carbon, ammonia water and hydrogen peroxide to perform one-pot reaction, and then mixing with concentrated hydrochloric acid to perform recrystallization to obtain [ Co (NH) 3 ) 6 ]Cl 3 @Co/C; the molar ratio of the hydrogen ions to the Co/C compound in the system after the Co/C compound, hydrochloric acid, ammonium chloride, activated carbon, ammonia water and hydrogen peroxide are mixed is 0.1-1:1; after the one-pot reactionThe mol ratio of chloride ions to Co/C compound in the system after being mixed with the concentrated hydrochloric acid is 0.2-2:1;
the [ Co (NH) 3 ) 6 ]Cl 3 Mixing @ Co/C, a chlorine-containing platinum source and water, and then dipping and evaporating to dryness to obtain a catalyst precursor;
and (3) annealing the catalyst precursor to obtain the supported catalyst.
5. The method of claim 4, wherein the manganese source comprises manganese chloride, the nitrogen source comprises melamine, the water is deionized water, and the surfactant comprises trimethyl 1-hexadecyl ammonium bromide or polyoxyethylene polyoxypropylene ether;
the molar ratio of the carbon carrier to the manganese source to the nitrogen source to the water is 1:0.001-0.05:0.001-0.05:1-40;
the molar ratio of the surfactant to the carbon carrier is 0.001-0.05:1;
the molar ratio of the ethyl orthosilicate to the carbon carrier is 0.1-5:1.
6. The preparation method according to claim 4, wherein the temperature rise rate to the temperature required for low-temperature sintering is 4-6 ℃/min, and the heat preservation time of the low-temperature sintering is 2-3 h;
the temperature rising rate of rising to the temperature required by high-temperature sintering is 4-6 ℃/min, and the heat preservation time of the high-temperature sintering is 2-3 h;
the molar ratio of the manganese and nitrogen doped mesoporous carbon to the cobalt chloride is 100-5:1;
the reduction is continuous flow microwave reduction, and the flow speed of the continuous flow microwave reduction is 50-500 mL/min.
7. The preparation method according to claim 4, wherein the mass ratio of the ammonium chloride to the Co/C composite is 1:1-10;
the mass ratio of the active carbon to the Co/C composite is 1:1-5;
the mass ratio of the ammonia water to the hydrogen peroxide to the Co/C composite is 1-5:1.
8. The method of claim 4, wherein the source of chloroplatinic acid comprises chloroplatinic acid, potassium chloroplatinate, ammonium hexachloroplatinate, potassium chloroplatinate, ammonium chloroplatinate, or sodium chloroplatinate;
the chlorine-containing platinum source and [ Co (NH) 3 ) 6 ]Cl 3 The mass ratio of @ Co/C is 10-1:1.
9. The preparation method according to claim 4, wherein the temperature of the annealing treatment is 700-800 ℃, the heating rate from the temperature required by the annealing treatment to the temperature required by the annealing treatment is 3-6 ℃/min, and the heat preservation time of the annealing treatment is 3-4 h; the annealing treatment is carried out in a mixed atmosphere of hydrogen and nitrogen, wherein the volume content of the hydrogen in the mixed atmosphere of the hydrogen and the nitrogen is 10-20%;
the annealing treatment further comprises the following steps:
sequentially carrying out acid washing and heat treatment on the annealed product to obtain the supported catalyst;
the pickling is to soak the annealed product in a nitric acid solution for 1-3 hours;
the temperature of the heat treatment is 380-420 ℃, the heating rate from the temperature required by the heat treatment to the temperature required by the heat treatment is 5-10 ℃/min, and the heat preservation time of the heat treatment is 2-3 h; the heat treatment is performed in a mixed atmosphere of hydrogen and nitrogen, and the volume content of the hydrogen in the mixed atmosphere of the hydrogen and the nitrogen is 10-20%.
10. Use of the supported catalyst according to any one of claims 1 to 3 or the supported catalyst prepared by the preparation method according to any one of claims 4 to 9 in proton exchange membrane fuel cells.
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| CN107362818A (en) * | 2017-07-12 | 2017-11-21 | 武汉理工大学 | Nitrogen phosphorus codope carbon coating transition metal diphosphide liberation of hydrogen catalyst and preparation method |
| CN113629259A (en) * | 2021-08-27 | 2021-11-09 | 中国人民解放军国防科技大学 | Preparation method of nitrogen-doped graphite carbon aerogel loaded Pt oxygen reduction electrocatalyst |
| WO2022196404A1 (en) * | 2021-03-19 | 2022-09-22 | パナソニックＩｐマネジメント株式会社 | Electrode catalyst, electrode catalyst layer using said electrode catalyst, membrane/electrode assembly, and electrochemical device |
| CN117352760A (en) * | 2023-11-05 | 2024-01-05 | 中国人民解放军国防科技大学 | Preparation method of multistage pore, nitrogen doped graphitized carbon supported platinum-based catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107362818A (en) * | 2017-07-12 | 2017-11-21 | 武汉理工大学 | Nitrogen phosphorus codope carbon coating transition metal diphosphide liberation of hydrogen catalyst and preparation method |
| WO2022196404A1 (en) * | 2021-03-19 | 2022-09-22 | パナソニックＩｐマネジメント株式会社 | Electrode catalyst, electrode catalyst layer using said electrode catalyst, membrane/electrode assembly, and electrochemical device |
| CN113629259A (en) * | 2021-08-27 | 2021-11-09 | 中国人民解放军国防科技大学 | Preparation method of nitrogen-doped graphite carbon aerogel loaded Pt oxygen reduction electrocatalyst |
| CN117352760A (en) * | 2023-11-05 | 2024-01-05 | 中国人民解放军国防科技大学 | Preparation method of multistage pore, nitrogen doped graphitized carbon supported platinum-based catalyst |
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